Prediction of the structures of hydrogen-bonded complexes using the laplacian of the charge density

Carroll, Marshall T.; Chang, C.; Bader, R. F. W.

doi:10.1080/00268978800100281

Cited by 247 publications

(78 citation statements)

References 32 publications

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“…This charge transfer is due to the polarization of the N 2 subunit by the electric ®eld of the proton donor. These results are consistent with the AIM analysis of Carroll et al [40], who found a very small charge transfer (0.0046e) for this complex. The pair covariance, CVNY VFY H, is small.…”

Section: The Weak and Medium Hydrogen-bonded Complexessupporting

confidence: 94%

“…This interpretation, based on physical arguments, challenges another opinion commonly held by the chemistry community and originally formulated by Legon and Millen [35,36] according to which the structure of hydrogen-bonded complexes is mostly driven by the location of the lone pair of the proton acceptor in the spirit of Gillespie's (VSEPR) model [37,38]. The analysis of the electron charge density within the theory of``Atoms in molecules'' (AIM) [39] provides a quantitative description of the electron redistribution as it enables the nucleophilic site of the base to be located [40,41].…”

Section: Introductionmentioning

confidence: 99%

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Does the topological approach characterize the hydrogen bond?

Fuster

Silvi

2000

Theoretical Chemistry Accounts: Theory, Computation, and Modeli

253

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The topological analysis of the electron localization function has been applied to complexes representative of the weak, medium and strong hydrogen bond. For both the weak and the medium hydrogen bonds, the number of basins in the complexes is the sum of those of the moieties. In this case, the formation of a weak or a medium hydrogen-bonded complex does not involve a chemical reaction. In the weak hydrogen bond case, the reduction of the localization domain yields two domains in the ®rst step, which can be partitioned afterwards into valence and core domains. In contrast, for medium complexes the core±valence separation is the ®rst event which occurs during the reduction process and therefore the complex should be considered as a single molecular species. Moreover, the analysis of the basin population variance indicates in this case a noticeable delocalization between the V(A, H) and V(B) basins. Finally, the symmetrical strong hydrogen bond has a protonated basin V(H) at the bond midpoint. Such a topology corresponds to an incomplete proton transfer and to a rather covalent bond.

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Section: The Weak and Medium Hydrogen-bonded Complexessupporting

confidence: 94%

Section: Introductionmentioning

confidence: 99%

Does the topological approach characterize the hydrogen bond?

Fuster

Silvi

2000

Theoretical Chemistry Accounts: Theory, Computation, and Modeli

253

View full text Add to dashboard Cite

show abstract

“…A bond mav be described as a shared interaction. where the degree of interaction may range from pure covalent to pure ionic and may include the weakly bonded interactions of interest in this study (7,(13)(14)(15). When a covalent bond forms, there is a lowering of the potential energy due to the increase in charge density between the two nuclei.…”

Section: Aim Propertiesmentioning

confidence: 99%

“…Tables 4 and 5 highlight the extended conjugation between the side chain and the ring atoms. According to studies on weak atomic interactions (14,15), the type of bonding found here between the S.-0 and H...O would be classified as a closed-shell interaction (Tables 2 and 3). The value of p, is typically an order of magnitude smaller than that for a covalent bond.…”

Section: Origin Of the Barrier ( A ) Hypervalentfi-bond Interactionsmentioning

confidence: 99%

Abinitio interpretation of conformer stabilization through bonding in the acetyl derivatives of two representative heterocyclic methine bases

Gough¹,

Millington²

1995

Can. J. Chem.

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Ab initio calculations (STO-3G and 3-21G* basis sets) have been performed on 2 and 3 to determine the most favorable structure and to provide an estimate of the barrier to internal rotation of the acyl group. The Zconfiguration is preferred in 2, the E configuration in 3, with calculated barriers to internal rotation of 79.9 and 68.7 kJ/mol, respectively, at the 3-21G* level. The wave functions from the 3-21G* calculations are analyzed with the theory of atoms in molecules. The identification of bond critical points characteristic of a closed shell interaction establishes the existence of a weak bond between S.-0 in 2 and between H.-0 in 3, for the preferred configurations. The energy required to break this bond as well as the loss of extended conjugation throughout the hetero ring and its side chain are responsible for the asymmetry in the barrier. These findings provide a theoretical explanation for experimental observations on this class of molecules in which one conformer is preferred to any other and only one crystal structure is identified.Key words: nonbonded sulfur-oxygen interaction, closed shell interaction, hydrogen bonding, 3-21G* basis set, theory of atoms in molecules.RCsumC : On a effectuC des calculs ab initio (ensembles de base STO-3G et 3-21G*) sur les composCs 2 et 3 dans le but de dkterminer leur structure la plus favorable et d'obtenir une evaluation de la barrikre a la rotation interne du groupe acyle. Les conformations prCfCrCes sont la Z pour le composC 2 et la conformation E pour le composC 3; au niveau 3-21G*, les bambres calculCes 21 la rotation interne sont respectivement de 79,9 et de 68,7 kJ mol-I. On a analysk les fonctions d'onde obtenues par les calculs au niveau 3-21G* a l'aide de la thCorie des atomes dans les molCcules. L'identification de points critiques dans les liaisons, caractCristiques d'une interaction a couche fermbe, permet d'ktablir que, dans les configurations prefkrkes, il existe une liaison faible entre S-0 dans le composC 2 et H-.O dans le composC 3. Ces rtsultats fournissent une explication thCorique des observations expkrimentales sur cette classe de molCcules dans lesquelles un conformbre est prCfCrC a tous les autres et avec lesquelles on n'identifie qu'une seule structure cristalline.

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“…A Lewis acid-base reaction corresponds to aligning a charge concentration (CC) on the base with a charge depletion (CD) on the acid, that is, by directing a vertex of the atomic graph on the base atom at a face of the polyhedron on the acid. This is a general phenomenon that is observed in many different kinds of interactions (I), examples being the formation of hydrogen bonds (13), the alignment of chlorine molecules in the solid (4), and the adsorption of molecules on surfaces (14)(15)(16). The Laplacian of the electronic density provides a physical model that guides one in the determination of the sites of adsorption and the geometry of approach of the substrate relative to the surface site, and predicts whether the interaction will correspond to physi-or chemisorption (14).…”

Section: Introductionmentioning

confidence: 99%

Study of NO and CO dissociation on the (100) Cu surface using density functional theory and the topological analysis of the electronic density and its Laplacian

Aray¹,

Rodríguez²

1996

Can. J. Chem.

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Molecular orbital ab initio Hartree-Fock, post-Hartree-Fock at the MP2 and QCISD levels, and density functional theory calculations of the dipole moment, the topology of the electronic density, p(r), and its Laplacian, VZp(r), for CO and NO molecules are reported. The results obtained confirm that density functional methods provide remarkably good electronic properties and a good description of the topology of p(r) and VZp(r). The Becke exchange functional with the correlation functional of Lee, Yang, and Parr was used to calculate the electronic density of the (100) Cu surface. Topological analysis of p(r) shows that the crystal graph corresponds to square pyramids between the atoms of the top of the surface and the atoms of the second layer. The topological analysis of -VZp shows that the atomic graph of the Cu surface exhibits one (3,-3) local charge concentration surrounded by four (3,+1) local charge depletion points. Additionally, there is a (3,+3) local depletion in the midpoint between each of four contiguous Cu atoms corresponding to the active site for the adsorption of the (3,-3) local charge concentration on the C atom of the CO or the N atom of the NO molecule. The larger value of the -VZp at the nonbonded charge concentration on the atoms and the geometrical configuration of these critical points favor the interaction of the NO over the CO molecule with the (100) Cu surface. This result is in accord with the known reaction barriers for these molecules.Key words: density functional theory, Laplacian of the electronic density, (100) Cu surface, carbon monoxide, nitrogen monoxide, molecular graph, atomic graph.RCsumC : Utilisant des calculs d'orbitales moltculaires ab initio de Hartree-Fock, aux niveaux post-Hartree-Fock MP2 et QCISD, et des calculs de la thkorie de la densit6 fonctionnelle, on a CvaluC les moments dipolaires et la topologie de la densite Clectronique, p(r) et son laplacien, V2p(r), des molCcules de CO et de NO. Les rtsultats obtenus confirment que les mCthodes de la densit6 fonctionnelle conduisent i des propriCtCs Clectroniques particulikrement bonnes ainsi qu'i une bonne description de la topologie de p(r) et de VZp(r). On a utilisC la fonctionnelle dlCchange de Becke avec la corrClation fonctionnelle de Lee, Yang et Parr pour calculer la densitt Clectronique de la surface (1 00) du Cu. L'analyse topologique de p(r) montre que le graphe du cristal correspond B des pyramides carries entre les atomes au sommet de la surface et les atomes de la deuxikme couche. L'analyse topologique de VZp montre que le graphe atomique de la surface du Cu prCsente une concentration locale de charge (3,-3) entourCeparquatrepoints(3,+l)prCsentant unedkficiencedecharge. Deplus, il y aunedificience localedecharge(3,+3) i la mi-distance entre chacun des quatre atomes de Cu contigus qui correspondent au site actif pour l'adsorption de la concentration locale de charge (3,-3) sur l'atome de carbone du Co ou sur l'atome d'azote de la molCcule de NO. La valeur plus Clevee du -VZp B la concentration d...

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Prediction of the structures of hydrogen-bonded complexes using the laplacian of the charge density

Cited by 247 publications

References 32 publications

Does the topological approach characterize the hydrogen bond?

Does the topological approach characterize the hydrogen bond?

Abinitio interpretation of conformer stabilization through bonding in the acetyl derivatives of two representative heterocyclic methine bases

Study of NO and CO dissociation on the (100) Cu surface using density functional theory and the topological analysis of the electronic density and its Laplacian

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